CN113166922A

CN113166922A - Metal film and sputtering target

Info

Publication number: CN113166922A
Application number: CN201980077161.1A
Authority: CN
Inventors: 岁森悠人; 野中庄平; 小见山昌三; 林雄二郎
Original assignee: Mitsubishi Materials Corp
Current assignee: Mitsubishi Materials Corp
Priority date: 2018-12-05
Filing date: 2019-12-05
Publication date: 2021-07-23
Also published as: TW202037728A; EP3892752A1; KR20210096120A; WO2020116558A1; JP2020090708A; EP3892752A4

Abstract

The present invention contains Cu in a range of 0.10 at% to 5.00 at%, and has a Pd content of 40 mass ppm or less, a Pt content of 20 mass ppm or less, an Au content of 20 mass ppm or less, an Rh content of 10 mass ppm or less, and a total content of Pd, Pt, Au and Rh of 50 mass ppm or less, with the remainder being composed of Ag and unavoidable impurities.

Description

Metal film and sputtering target

Technical Field

The present invention relates to a metal film used as a reflective film, an electrode film, or a wiring film, and a sputtering target used for forming the metal film.

The present application claims priority based on patent application No. 2018-228367, filed in japanese application on 12/5/2018, and the contents thereof are incorporated herein.

Background

For example, as a reflective film, an electrode film, and a wiring film of a display device such as a liquid crystal display, an organic EL display, or a touch panel, for example, a metal film made of Ag or an Ag alloy is proposed as shown in patent document 1.

Further, patent documents 2 to 4 each apply a laminated film having a laminated structure of a transparent conductive oxide film and a metal film made of Ag or an Ag alloy.

As shown in patent documents 1 to 4, the reflective film, the electrode film, and the wiring film are formed into a predetermined pattern by, for example, wet etching using an etching solution (hereinafter referred to as etching).

Here, when a metal film made of Ag or an Ag alloy is subjected to etching treatment, for example, an etching solution containing nitric acid such as PAN (phosphoric acid + nitric acid + acetic acid) is generally used.

However, when a metal film made of Ag or an Ag alloy is etched with an etching solution containing nitric acid, the dissolution rate of Ag is extremely high, and therefore, it may be difficult to control the etching state with high accuracy.

Further, when the laminated film of the transparent conductive oxide film and the metal film is subjected to etching treatment with an etching solution containing nitric acid, there is a problem that the difference in etching rates between the transparent conductive oxide film and the metal film is large, the metal film is over-etched, and the pattern shape after etching cannot be formed with high accuracy.

Here, patent document 2 proposes a method of suppressing overetching of a metal film by using an oxalic acid etching solution.

Patent documents

3 and 4 propose the following methods: the composition of the transparent conductive oxide film is defined so as to reduce the difference in etching rate between the transparent conductive oxide film and the metal film, thereby suppressing overetching of the metal film.

Patent document 1: japanese laid-open patent publication No. 2006-028641 (A)

Patent document 2: japanese patent No. 6020750 (B)

Patent document 3: japanese laid-open patent publication No. 2017-179594 (A)

Patent document 4: japanese laid-open patent publication No. 2017-183274 (A)

However, in the step of etching a metal film made of Ag or an Ag alloy, since an etching solution containing nitric acid such as PAN has been widely used conventionally as described above, it is likely that the etching treatment needs to be performed with high accuracy by using the etching solution containing nitric acid.

Further, depending on the characteristics required for the laminated film, the transparent conductive oxide film described in

patent documents

3 and 4 may not be applicable.

Therefore, even when an etching solution containing nitric acid such as PAN is used, a metal film which can suppress the etching rate is required.

In addition, in the metal film made of Ag or an Ag alloy, Ag is likely to agglomerate by heat, and therefore, for example, there is a possibility that an agglomeration protrusion (hillock) is generated by heating in the process, or the electrical characteristics or optical characteristics of the metal film are deteriorated by agglomeration in a hot and humid environment.

Disclosure of Invention

The present invention has been made in view of the above circumstances, and an object thereof is to provide a metal film which can suppress the etching rate even when an etching solution containing nitric acid is used, can perform etching treatment with high accuracy, and can suppress aggregation of Ag due to heat, and a sputtering target used for forming the metal film.

As a result of intensive studies to solve the above problems, the present inventors have found that aggregation of Ag due to heat can be suppressed by adding an appropriate amount of Cu to a metal film.

Further, the following findings were obtained with respect to the etching rate of the metal film.

When a metal film made of Ag or an Ag alloy is etched with an etching solution containing nitric acid, a dissolution reaction of Ag and a reduction reaction of nitric acid proceed. At this time, if the reduction reaction of nitric acid is promoted, the dissolution reaction of Ag is also promoted, and the etching rate becomes fast. Therefore, by limiting the contents of elements such as Pd, Pt, Au, Rh which act as catalysts in the reduction reaction of nitric acid, the etching rate of the metal film can be suppressed even with the use of the etching liquid containing nitric acid.

The present invention has been made based on the above findings, and a metal film of the present invention is characterized by containing Cu in a range of 0.10 atomic% or more and 5.00 atomic% or less, and having a Pd content of 40 mass ppm or less, a Pt content of 20 mass ppm or less, an Au content of 20 mass ppm or less, an Rh content of 10 mass ppm or less, and a total content of Pd, Pt, Au, and Rh of 50 mass ppm or less, with the remainder being composed of Ag and unavoidable impurities.

In the metal film having such a configuration, Cu is contained in a range of 0.10 atomic% or more and 5.00 atomic% or less, and therefore aggregation of Ag due to heat can be suppressed, and heat resistance of the metal film can be improved.

In the metal film of the present invention, the contents of Pd, Pt, Au, and Rh that function as a catalyst in the reduction reaction of nitric acid are limited as described above, and therefore, even when etching treatment is performed using an etching solution containing nitric acid, excessive dissolution reaction of Ag can be suppressed, and the etching rate can be suppressed.

Therefore, even if the etching treatment is performed using the etching solution containing nitric acid, the etching state can be stably controlled, and the pattern shape can be formed with high precision.

Here, in the metal film of the present invention, at least one or two or more of Sb, Zn, Sn, Pb, and Ti may be further contained as an additive element in a total amount of 0.05 atomic% or more, and the total content of Cu and Sb, Zn, Sn, Pb, and Ti may be 5.00 atomic% or less.

Sb, Zn, Sn, Pb, and Ti act as catalytic poisons (catalyst poisons) for suppressing the reduction reaction of nitric acid, and therefore, by containing these additive elements in the above-described ranges, the reduction reaction of nitric acid can be further suppressed, and the etching rate of the metal film can be further suppressed.

The sputtering target of the present invention contains Cu in a range of 0.10 atomic% to 5.00 atomic%, and has a Pd content of 40 mass ppm or less, a Pt content of 20 mass ppm or less, an Au content of 20 mass ppm or less, an Rh content of 10 mass ppm or less, and a total content of Pd, Pt, Au, and Rh of 50 mass ppm or less, with the remainder being composed of Ag and unavoidable impurities.

In the sputtering target having this configuration, Cu is contained in a range of 0.10 atomic% or more and 5.00 atomic% or less, and therefore aggregation of Ag due to heat can be suppressed, and a metal film having excellent heat resistance can be formed.

In the sputtering target of the present invention, the contents of Pd, Pt, Au, and Rh that act as catalysts in the reduction reaction of nitric acid are limited as described above, and therefore, the contents of Pd, Pt, Au, and Rh can be limited in the formed metal film, and even if the etching treatment is performed using an etching solution containing nitric acid, a metal film in which the etching rate can be suppressed can be formed.

Here, the sputtering target of the present invention may further contain at least one or two or more of Sb, Zn, Sn, Pb, and Ti as an additive element in a total amount of 0.05 atomic% or more, and the total content of Cu and Sb, Zn, Sn, Pb, and Ti may be 5.00 atomic% or less.

In this case, since Sb, Zn, Sn, Pb, and Ti which function as catalytic poisons for suppressing the reduction reaction of nitric acid are contained, these additive elements are contained in the metal film to be formed in the above range, whereby the reduction reaction of nitric acid can be further suppressed, and even if the etching treatment is performed using the nitric acid-containing etching solution, the metal film which can suppress the etching rate can be formed.

In the sputtering target of the present invention, it is preferable that the average value μ of the total content values of Sb, Zn, Sn, Pb, and Ti at a plurality of measurement points on the sputtering surface is determined_TAnd standard deviation sigma_TCalculated distribution D_T＝(σ_T/μ_T) X 100 (%) is 20% or less.

When the sputtering target contains additional elements such as Sb, Zn, Sn, Pb and Ti, the average value mu of the total content of the additional elements at a plurality of measurement points on the sputtering surface is determined_TAnd standard deviation sigma_TCalculated distribution D_TSince the content of the additive elements is controlled to 20% or less, the additive elements are uniformly present on the sputtering surface, and a metal film in which the additive elements are uniformly dispersed can be stably formed.

According to the present invention, it is possible to provide a metal film which can suppress the etching rate even when an etching solution containing nitric acid is used, can perform etching treatment with high accuracy, and can suppress Ag aggregation caused by heat, and a sputtering target used for forming the metal film.

Drawings

Fig. 1 is an explanatory view showing measurement positions of the content of an additive element on a sputtering surface of a rectangular flat plate-type sputtering target.

Fig. 2 is an explanatory view showing the measurement positions of the content of the additive elements on the sputtering surface of the disc-shaped sputtering target.

Fig. 3A is an explanatory view showing a measurement position of the content of the additive element on the sputtering surface of the cylindrical sputtering target, and is a cross-sectional view orthogonal to the axis.

Fig. 3B is an explanatory view showing a measurement position of the content of the additive element on the sputtering surface of the cylindrical sputtering target, and is a cross-sectional view taken along the axis.

Detailed Description

The metal film and the sputtering target according to one embodiment of the present invention will be described below.

The metal film of the present embodiment is used as a reflective film, an electrode film, or a wiring film of a display device such as a liquid crystal display, an organic EL display, or a touch panel.

< Metal film >

The metal film according to the embodiment of the present invention has a composition containing Cu in a range of 0.10 atomic% to 5.00 atomic% inclusive, and has a Pd content of 40 mass ppm or less, a Pt content of 20 mass ppm or less, an Au content of 20 mass ppm or less, an Rh content of 10 mass ppm or less, and a total content of Pd, Pt, Au, and Rh of 50 mass ppm or less, with the remainder being composed of Ag and unavoidable impurities.

In the metal film of the present embodiment, at least one or two or more of Sb, Zn, Sn, Pb, and Ti may be further contained as an additive element in a total amount of 0.05 atomic% or more, and the total content of Cu and Sb, Zn, Sn, Pb, and Ti may be 5.00 atomic% or less.

Here, the reason why the composition of the metal film of the present embodiment is defined as described above will be described.

(Cu)

Cu has an effect of suppressing diffusion and movement of Ag atoms and suppressing aggregation of Ag in the metal film.

When the Cu content is less than 0.10 atomic%, the above-described effect may not be exhibited. On the other hand, when the Cu content exceeds 5.00 atomic%, there is a possibility that the optical characteristics and the electrical characteristics are deteriorated.

Based on the above, in the present embodiment, the content of Cu in the metal film is set in the range of 0.10 atomic% or more and 5.00 atomic% or less.

In order to reliably suppress aggregation of Ag by heat, the lower limit of the Cu content is preferably 0.10 atomic% or more, and more preferably 0.20 atomic% or more.

In order to reliably suppress deterioration of optical characteristics and electrical characteristics, the upper limit of the Cu content is preferably 4.00 atomic% or less, and more preferably 3.00 atomic% or less.

(Pd、Pt、Au、Rh)

The elements such as Pd, Pt, Au, and Rh described above function as catalysts in the reduction reaction of nitric acid, and promote the reduction reaction of nitric acid. At the same time, the dissolution reaction of Ag is also promoted, and thus the etching rate of the metal film becomes fast.

Therefore, the contents of Pd, Pt, Au, Rh are limited as described above, whereby the etching rate of the metal film can be suppressed even with the use of the etching liquid containing nitric acid.

Here, the content of Pd is preferably 10 mass ppm or less, the content of Pt is preferably 5 mass ppm or less, the content of Au is preferably 5 mass ppm or less, and the content of Rh is preferably 2 mass ppm or less. Further, the total content of Pd, Pt, Au, and Rh is preferably 10 mass ppm or less.

Although not particularly limited, the lower limit of the content of each of Pd, Pt, Au, and Rh in the metal film may be set to more than 0.1 mass ppm. The lower limit of the total content of Pd, Pt, Au and Rh may be set to 0.5 mass ppm or more.

(Sb、Zn、Sn、Pb、Ti)

The additive elements (Sb, Zn, Sn, Pb, and Ti) function as catalytic poisons in the reduction reaction of nitric acid to suppress the reduction reaction of nitric acid, and thus may be added as needed.

Here, by setting the total content of Sb, Zn, Sn, Pb, and Ti to 0.05 atomic% or more, the reduction reaction of nitric acid can be sufficiently suppressed, and the etching rate of the metal film can be further suppressed even when an etching solution containing nitric acid is used. On the other hand, by setting the total content of Cu, Sb, Zn, Sn, Pb, and Ti to 5.00 atomic% or less, it is possible to suppress a large change in the characteristics of the metal film.

Therefore, in the present embodiment, when the above-described additive elements (Sb, Zn, Sn, Pb, and Ti) are added, the lower limit of the total content of the additive elements (Sb, Zn, Sn, Pb, and Ti) is set to 0.05 atomic% or more, and the total content of Cu, Sb, Zn, Sn, Pb, and Ti is set to 5.00 atomic% or less.

Here, the lower limit of the total content of the above-mentioned additive elements (Sb, Zn, Sn, Pb, and Ti) is preferably 0.10 atomic% or more, and more preferably 0.20 atomic% or more. The upper limit of the total content of Cu and the additive elements (Sb, Zn, Sn, Pb, and Ti) is preferably 4.00 atomic% or less, and more preferably 3.00 atomic% or less.

In the case where the above-mentioned additive elements (Sb, Zn, Sn, Pb, Ti) are not intentionally added, the above-mentioned additive elements may be contained as impurities in an amount of less than 0.05 atomic% in total.

< sputtering target >

Next, the sputtering target of the present embodiment will be explained. This sputtering target is used for forming the metal film of the present embodiment described above.

The sputtering target of the present embodiment has a composition containing Cu in a range of 0.10 atomic% or more and 5.00 atomic% or less, and having a Pd content of 40 mass ppm or less, a Pt content of 20 mass ppm or less, an Au content of 20 mass ppm or less, an Rh content of 10 mass ppm or less, and a total content of Pd, Pt, Au, and Rh of 50 mass ppm or less, with the remainder being composed of Ag and unavoidable impurities.

Although not particularly limited, the lower limit values of Pd, Pt, Au, and Rh in the sputtering target may be set to be more than 0.1 mass ppm.

In the sputtering target of the present embodiment, at least one or two or more of Sb, Zn, Sn, Pb, and Ti may be further contained as an additive element in a total amount of 0.05 atomic% or more, and the total content of Cu and Sb, Zn, Sn, Pb, and Ti is 5.00 atomic% or less.

In the sputtering target of the present embodiment, when at least one or two or more of Sb, Zn, Sn, Pb, and Ti are contained as the additive element in a total amount of 0.05 atomic% or more, it is preferable that the average value μ of the total content values of the additive elements (Sb, Zn, Sn, Pb, and Ti) in the plurality of measurement points of the sputtering surface is determined based on the average value μ_TAnd standard deviation sigma_TAnd a distribution D calculated by the following formula_TIs 20% or less.

D_T＝(σ_T/μ_T)×100(％)

Although not particularly limited, the distribution D_TThe lower limit of (3) may be 0.2% or more.

Here, the reason why the composition and the distribution of the additive elements are defined in the sputtering target of the present embodiment as described above will be described.

(composition of ingredients)

The sputtering target of the present embodiment is used for forming the metal film described above, and is set according to the composition of the metal film of the present embodiment described above.

Therefore, in the sputtering target of the present embodiment, Cu is contained in a range of 0.10 atomic% or more and 5.00 atomic% or less in order to form a metal film which suppresses aggregation of Ag and has excellent heat resistance.

As described above, the sputtering target of the present embodiment limits the contents of Pd, Pt, Au, and Rh, which are elements that function as catalysts in the reduction reaction of nitric acid, in order to form a metal film that suppresses the etching rate.

Further, in the case of the additive elements (Sb, Zn, Sn, Pb, Ti) that act as catalytic poisons in the reduction reaction containing nitric acid, the total content of these additive elements is defined as described above.

(distribution of additive elements (Sb, Zn, Sn, Pb, Ti))

When the sputtering target of the present embodiment contains the above-described additive elements (Sb, Zn, Sn, Pb, and Ti), the metal film to be formed also contains the above-described additive elements.

Here, the average value μ of the total content values of the additive elements (Sb, Zn, Sn, Pb, Ti) at a plurality of measurement points on the sputtering surface is determined_TAnd standard deviation sigma_TCalculated distribution D_TWhen the content is 20% or less, the additive elements uniformly exist in the sputtering surface, and a metal film in which the additive elements are uniformly dispersed can be formed, so that the etching rate becomes stable as a whole of the metal film.

The average value μ of the total content values of the additive elements (Sb, Zn, Sn, Pb, Ti) was determined_TAnd standard deviation sigma_TCalculated distribution D_TPreferably 15% or less, more preferably 10% or less.

In the case of a sputtering target having a rectangular sputtering surface, as shown in fig. 1, it is preferable that the content of the additive element is measured at a plurality of 5 points including at least an intersection (1) intersecting a diagonal line and corners (2), (3), (4), and (5) on each diagonal line on the sputtering surface. The corners (2), (3), (4), and (5) are provided within 10% of the total length of the diagonal line from the corner to the inside.

In the case of a sputtering target having a circular sputtering surface, as shown in fig. 2, the content of the additive element is preferably measured at 5 points on the sputtering surface, the 5 points including at least the center (1) of the circle and the outer peripheral portions (2), (3), (4), and (5) on 2 straight lines passing through the center of the circle and intersecting perpendicularly to each other. The outer peripheral portions (2), (3), (4), and (5) are provided within a range of 10% or less of the diameter from the outer peripheral edge toward the inside.

Further, as shown in fig. 3A and 3B, in the cylindrical sputtering target having a cylindrical sputtering surface, the content of the additive element is preferably measured at a plurality of total 12 points including at least one end portion, a central portion, and the other end portion in the axial direction at intervals of 90 ° in the outer circumferential direction of (1), (2), (3), and (4). The one end and the other end in the axial direction are provided within 10% of the total length in the axial direction from the one end in the axial direction toward the inside.

< method for producing sputtering target >

Next, a method for manufacturing a sputtering target according to the present embodiment will be described.

First, an Ag raw material with reduced Pd, Pt, Au, and Rh contents was prepared.

In the present embodiment, Ag having a purity of 99.9 mass% or more is subjected to electrolytic refining to produce electrodeposited Ag, and the obtained electrodeposited Ag is used again as an anode for electrolysis to be subjected to casting and re-electrolysis. This process is repeated to reduce the impurity concentration in Ag. Further, each time electrolytic refining is performed, composition analysis is performed by ICP emission spectrometry.

Thus, an Ag raw material is obtained in which the Pd content is limited to 40 mass ppm or less, the Pt content is 20 mass ppm or less, the Au content is 20 mass ppm or less, the Rh content is 10 mass ppm or less, and the total content of Pd, Pt, Au and Rh is 50 mass ppm or less.

Then, a Cu raw material having a purity of 99.9 mass% or more was prepared.

Further, when Sb, Zn, Sn, Pb, and Ti are contained as additive elements, an Sb raw material, a Zn raw material, an Sn raw material, a Pb raw material, and a Ti raw material having a purity of 99.9 mass% or more are prepared, respectively. As the raw material, an Ag master alloy containing Cu and additive elements (Sb, Zn, Sn, Pb, Ti) may be used.

Next, the Ag raw material is melted in a high vacuum or an inert gas atmosphere using a melting furnace, and the Cu raw material and, if necessary, the Sb raw material, the Zn raw material, the Sn raw material, the Pb raw material, and the Ti raw material are added to the obtained Ag melt. Thereafter, the melting is performed under a high vacuum or an inert gas atmosphere. Here, in order to make the concentration of the additive element uniform in the ingot, it is preferable to perform melting by a high-frequency induction heating furnace capable of stirring the solution at a high frequency.

It is preferable that the Ag raw material is melted by once evacuating the interior of the melting furnace to a high vacuum, then performing the melting in an atmosphere replaced with Ar, and then charging the sub-raw material in an Ar atmosphere.

Then, the Ag melt is poured into a mold having a predetermined shape to form an Ag ingot. In order to eliminate the segregation of the added elements as much as possible when the Ag melt is cast, it is preferable to rapidly cool the Ag melt by pouring into a mold after water cooling.

Next, the obtained Ag ingot was forged and rolled. The rolling is carried out by hot rolling or cold rolling.

When hot rolling is used, the homogenization heat treatment step before the start of rolling is preferably a heat treatment performed at a temperature of 600 ℃ to 700 ℃ for 1 hour to 10 hours. If the temperature is less than 600 ℃, homogenization may become insufficient, and if the temperature exceeds 700 ℃, a liquid phase may appear in the ingot, and the target may be softened/melted. When the heat treatment time is less than 1 hour, homogenization may be insufficient, and when it exceeds 10 hours, internal oxidation may occur.

The atmosphere in the above-mentioned homogenizing heat treatment step is not particularly limited, and may be, for example, an atmospheric atmosphere or an inert gas atmosphere.

The hot rolling is performed after the homogenization heat treatment step, but the temperature at the end of the rolling is preferably 400 ℃ or higher and 700 ℃ or lower, and in some cases, it is preferable to add intermediate annealing.

In the rolling, the cumulative rolling reduction is preferably 70% or more, and the rolling reduction in at least the last 1 pass of the rolling is preferably 20% or more. If the rolling reduction is less than 20%, the grain size is not sufficiently refined, and the grain size is not sufficiently homogenized in the interior. In addition, it is substantially difficult to achieve a reduction ratio of 50% or more per 1 pass due to the capacity of the rolling mill.

After rolling, heat treatment is performed to uniformize the crystal structure of the target material and to remove the crystal structure by work solidification. The heat treatment is preferably performed under the condition that the heat treatment temperature is in the range of 500 ℃ to 700 ℃ and kept for 1 hour to 5 hours. If the temperature is less than 500 ℃, the effect of work-hardening removal is insufficient, and if the temperature exceeds 700 ℃, crystal grains may be coarsened, or a liquid phase may appear and the target may be melted/softened. When the heat treatment time is less than 1 hour, homogenization becomes insufficient. After the heat treatment, the steel sheet is rapidly cooled by air cooling or water cooling.

The atmosphere in the heat treatment is not particularly limited, and may be, for example, an atmospheric atmosphere or an inert gas atmosphere.

Then, cutting or the like is performed to obtain a predetermined shape and size.

The sputtering target of the present embodiment is manufactured through the above-described steps.

< method for producing metal film >

Next, a method for producing a metal film according to the present embodiment will be described.

The metal film of the present embodiment can be formed by sputtering using the sputtering target of the present embodiment described above.

The sputtering target is bonded to a back plate made of, for example, oxygen-free copper, and mounted on a sputtering apparatus, thereby forming a film on the surface of the substrate by sputtering.

Here, the sputtering apparatus used may be a stationary opposed type in which the substrate on which the metal film is formed is stationary and sputtering is performed, or a substrate transport type (continuous-line) in which the substrate is transported and sputtered.

As a power source of the sputtering apparatus, for example, a Direct Current (DC) power source, a high frequency (RF) power source, an intermediate frequency (MF) power source, or an Alternating Current (AC) power source can be used.

According to the metal film of the present embodiment configured as described above, since Cu is contained in the range of 0.10 atomic% or more and 5.00 atomic% or less, aggregation of Ag due to heat can be suppressed, and the heat resistance of the metal film can be improved.

Then, the metal film of the present embodiment has the following composition: since the content of Pd is 40 mass ppm or less, the content of Pt is 20 mass ppm or less, the content of Au is 20 mass ppm or less, the content of Rh is 10 mass ppm or less, and the total content of Pd, Pt, Au and Rh is 50 mass ppm or less, and the remainder is made up of Ag and unavoidable impurities, the content of elements such as Pd, Pt, Au and Rh which act as a catalyst in the reduction reaction of nitric acid is limited, and even when etching treatment is performed using a nitric acid-containing etching solution such as PAN, excessive dissolution reaction of Ag can be suppressed, and the etching rate can be suppressed. Therefore, the etching state can be stably controlled, and the pattern shape can be formed with high accuracy.

Furthermore, in the metal film of the present embodiment, when at least one or two or more of Sb, Zn, Sn, Pb, and Ti are further contained as an additive element in a total amount of 0.05 atomic% or more, and the total content of Cu and Sb, Zn, Sn, Pb, and Ti is set to 5.00 atomic% or less, the additive element described above functions as a catalytic poison that suppresses the reduction reaction of nitric acid, and can further suppress the reduction reaction of nitric acid, thereby suppressing the excessive progress of the dissolution reaction of Ag, and further suppressing the etching rate.

In the sputtering target of the present embodiment, Cu is contained in a range of 0.10 atomic% or more and 5.00 atomic% or less, and therefore aggregation of Ag due to heat can be suppressed, and a metal film having excellent heat resistance can be formed.

The sputtering target of the present embodiment has the following composition: since the content of Pd is 40 mass ppm or less, the content of Pt is 20 mass ppm or less, the content of Au is 20 mass ppm or less, the content of Rh is 10 mass ppm or less, and the total content of Pd, Pt, Au, and Rh is 50 mass ppm or less, and the remainder is made up of Ag and unavoidable impurities, a metal film that can suppress the etching rate can be formed even when etching treatment is performed using a nitric acid-containing etching liquid such as PAN as described above.

Further, in the sputtering target of the present embodiment, when at least one or two or more of Sb, Zn, Sn, Pb, and Ti are further contained as additive elements in a total amount of 0.05 atomic% or more, and the total content of Cu and Sb, Zn, Sn, Pb, and Ti is 5.00 atomic% or less, even when etching treatment is performed using an etching solution containing nitric acid such as PAN, a metal film capable of further suppressing the etching rate can be formed.

Then, in the sputtering target of the present embodiment, at least one or two or more of Sb, Zn, Sn, Pb, and Ti is contained as an additive element in a total amount of 0.05 atomic% or more, and an average value μ of the total content values of Sb, Zn, Sn, Pb, and Ti at a plurality of measurement points on the sputtering surface is determined_TAnd standard deviation sigma_TCalculated distribution D_TWhen the content is 20% or less, the additive elements are uniformly present on the sputtering surface, and a metal film in which the additive elements are uniformly dispersed can be formed, so that the etching rate can be stabilized over the entire metal film.

The embodiments of the present invention have been described above, but the present invention is not limited to these embodiments, and can be modified as appropriate within a range not departing from the technical spirit of the present invention.

The metal film of the present invention can be used as a single film, or can be used as a laminated film with another film such as a conductive oxide film.

In the present embodiment, the case where the sputtering target is manufactured by hot rolling and cold rolling an Ag ingot has been described, but the present invention is not limited thereto, and other processing methods such as hot forging may be applied. As for the processing method, a known method is preferably selected as appropriate in accordance with the shape of the sputtering target to be manufactured.

Examples

The results of the confirmation experiment performed to confirm the effectiveness of the present invention will be described below.

By repeating the electrolytic refining and performing the component analysis by ICP emission spectrometry, an Ag raw material is obtained in which the Pd content is limited to 40 mass ppm or less, the Pt content is 20 mass ppm or less, the Au content is 20 mass ppm or less, the Rh content is 10 mass ppm or less, and the total content of Pd, Pt, Au, and Rh is 50 mass ppm or less. In comparative examples 3 to 8, Ag materials with unlimited contents of the above elements were used.

The Ag raw material is melted in a vacuum atmosphere, replaced with Ar gas, and then added with a Cu raw material having a purity of 99.9 mass% or more, and if necessary, an Sb raw material having a purity of 99.9 mass% or more, a Zn raw material, an Sn raw material, a Pb raw material, and a Ti raw material, and melted into an Ag melt having a predetermined composition. Then, the Ag melt is cast to produce an Ag ingot.

(composition of ingredients)

From the obtained Ag ingot, a sample for analysis was extracted, and the composition was measured by ICP emission spectroscopy. The measurement results are shown in table 1 as the composition of the sputtering target.

In table 1, the contents of elements (catalyst elements) such as Pd, Pt, Au, and Rh which act as catalysts in the reduction reaction of nitric acid are shown by mass ratio, and the contents of Cu and additive elements (Sb, Zn, Sn, Pb, and Ti) are shown by atomic ratio.

The obtained Ag ingot was hot-rolled. The rolling start temperature was set to 650 ℃, the rolling end temperature was set to 400 ℃, and the cumulative rolling reduction was set to 80%.

After hot rolling, the steel sheet was heat-treated at 600 ℃ for 1 hour. After the heat treatment, the steel sheet is rapidly cooled by water cooling.

Thus, a plate material having a length of 2000mm, a width of 200mm and a thickness of 8mm was obtained.

(distribution of additive elements)

In the obtained sputtering target, the average value μ of the total content of the additive elements in the sputtering surface was measured as follows_TAnd standard deviation sigma_TAnd distribution D_T。

The total content of the added elements was measured by extracting measurement samples from the positions shown in fig. 1 and performing ICP-MS analysis using the respective measurement samples.

From the total content of the additive elements obtained from the measurement samples at 5 points, the average value μ of the total content of the additive elements was calculated as the whole sputtering target_TAnd standard deviation sigma_T. Then, these average values μ are used_TAnd standard deviation sigma_TCalculating a distribution D_T＝(σ_T/μ_T) X 100 (%). The measurement results are shown in table 1.

Next, the sputtering target was welded to a back plate made of oxygen-free copper, and the back plate was mounted on a sputtering apparatus. In the present embodiment, a magnetron DC sputtering apparatus is used. In this embodiment, a substrate transport type sputtering apparatus is used.

Next, the plate material was cut and machined to produce a sputtering target having a predetermined size (126mm × 178mm × 6mm in thickness).

The sputtering target obtained as described above was welded to a backing plate made of oxygen-free copper, and was mounted on a sputtering apparatus. In the present embodiment, a magnetron DC sputtering apparatus is used. In the present embodiment, a substrate-carrying type sputtering apparatus is used which carries out sputtering while carrying a substrate.

Then, sputtering was performed under the following conditions to form a metal film on a glass substrate (EAGLE XG manufactured by Corning Incorporated).

Film formation starting vacuum degree: 1.0X 10^-4Pa or less

Sputtering gas: high purity argon

Sputtering gas pressure in the chamber: 0.4Pa

Direct current power: 100W

(composition of Metal film)

Under the above conditions, a metal film was formed on a glass substrate to a thickness of 1000nm, and the composition thereof was measured by ICP emission spectrometry. As a result, it was confirmed that the composition was equivalent to that of a sputtering target, and that in inventive examples 1 to 25, the Cu content was 0.10 atomic% or more and 5.00 atomic% or less, the Pd content was 40 mass ppm or less, the Pt content was 20 mass ppm or less, the Au content was 20 mass ppm or less, the Rh content was 10 mass ppm or less, and the total content of Pd, Pt, Au, and Rh was 50 mass ppm or less, and in inventive examples 8 to 25, the total content of Sb, Zn, Sn, Pb, and Ti was 0.05 atomic% or more, and the total content of Cu, Sb, Zn, Sn, Pb, and Ti was 5.00 atomic% or less.

(measurement of film thickness)

Under the above conditions, a metal film having a thickness of 100nm was formed on the glass substrate. In the case of film formation by sputtering, the film thickness is measured by a step profiler (DEKTAK-XT) at a constant film formation time to measure the sputtering rate, and the film formation time is adjusted based on the value to obtain a target film thickness.

The cross section of the actual metal film was observed by a Transmission Electron Microscope (TEM) to confirm whether or not the film was formed to a film thickness that satisfies the target value. For sample preparation for TEM observation, for example, a cross-section polisher (CP) or a Focused Ion Beam (FIB) can be used.

Then, the metal film formed as described above was evaluated for electrical characteristics, heat resistance, and etching characteristics as follows.

(evaluation of Electrical characteristics)

The sheet resistance of the metal film was measured by a four-probe method based on a resistance measuring instrument Loresta GP manufactured by Mitsubishi Chemical Corporation.

(Heat resistance)

The heat treatment was performed on the metal film after the film formation to evaluate the heat resistance of the metal film. The heat treatment was carried out at 250 ℃ for 1 hour in an atmospheric atmosphere. The metal film after the heat treatment was observed with an optical microscope to confirm the presence or absence of hillock (protrusion).

(evaluation of etching characteristics)

First, a wiring pattern was formed by photolithography on a metal film having a thickness of 100nm formed on a glass substrate.

A photoresist (OFPR-8600 manufactured by Tokyo Ohka Kogyo co., ltd.) was coated by a spin coater, pre-baked at 110 ℃ (pre-bake) followed by exposure, and then the pattern was developed by a developing solution (NMD-W manufactured by Tokyo Ohka Kogyo co., ltd.) followed by post-baking at 150 ℃ (post-bake). Thus, a comb-shaped wiring pattern having a width of 100 μm and an interval of 100 μm was formed on the Ag alloy film.

The film is wet-etched. As the etching solution, SEA-2 manufactured by Kanto Chemical co., inc. was used, and etching was performed at a liquid temperature of 40 ℃ for an immersion time of 30 seconds.

The wiring film obtained in the above manner was cleaved to observe the cross section of the wiring, and the cross section was observed by SEM (scanning electron microscope). Then, the difference between the parallel positions of the Ag film edge and the photoresist edge observed by SEM was measured as the amount of over-etching of the Ag film.

[ Table 1]

[ Table 2]

In comparative example 101 formed using the sputtering target of comparative example 1 having a Cu content of 0.01 atomic%, aggregation of Ag due to heat was not suppressed, and hillocks were observed after the heat treatment.

In comparative example 102 formed using the sputtering target of comparative example 2 having a Cu content of 7.00 atomic%, the sheet resistance was high, and the electrical characteristics of the metal film could not be secured.

In comparative example 103 formed using the sputtering target of comparative example 3 having a Pd content of 55.0 mass ppm, comparative example 104 formed using the sputtering target of comparative example 4 having a Pt content of 30.0 mass ppm, comparative example 105 formed using the sputtering target of comparative example 5 having an Au content of 30.0 mass ppm, and comparative example 106 formed using the sputtering target of comparative example 6 having an Rh content of 15.0 mass ppm, the over-etching amount was large and 1.8 to 2.0 μm, and the etching characteristics were insufficient.

In comparative example 107 formed using the sputtering target of comparative example 7 in which the total content of Pd, Pt, Au, and Rh was 65.0 mass ppm, and comparative example 108 formed using the sputtering target of comparative example 8 in which the total content of Pd, Pt, Au, and Rh was 240.0 mass ppm, the over-etching amount was large, 1.8 to 3.0 μm, and the etching characteristics were insufficient.

Furthermore, in comparative examples 109 to 113 formed using the sputtering targets of comparative examples 9 to 13 in which the total content of Cu and Sb, Zn, Sn, Pb, and Ti as additive elements exceeded 5.00 atomic%, all sheet resistances increased, and the electrical characteristics of the metal film could not be ensured.

On the other hand, in invention examples 101 to 107 formed using the sputtering targets of invention examples 1 to 7 containing Cu in the range of 0.10 atomic% to 5.00 atomic%, with the Pd content of 40 mass ppm or less, the Pt content of 20 mass ppm or less, the Au content of 20 mass ppm or less, the Rh content of 10 mass ppm or less, the total content of Pd, Pt, Au, and Rh of 50 mass ppm or less, and the balance made up of Ag and unavoidable impurities, the overetching amount was suppressed low, and the etching characteristics were excellent. Further, the sheet resistance is sufficiently low, and the electrical characteristics of the metal film can be ensured. Further, no hillock was observed after the heat treatment, and the heat resistance was excellent.

Further, in invention examples 108 to 125 formed using the sputtering target of invention examples 8 to 25 in which Cu was contained in a range of 0.10 atomic% or more and 5.00 atomic% or less, Pd was 40 mass ppm or less, Pt was 20 mass ppm or less, Au was 20 mass ppm or less, Rh was 10 mass ppm or less, and the total content of Pd, Pt, Au, and Rh was 50 mass ppm or less, and further at least one or two or more of Sb, Zn, Sn, Pb, and Ti was contained as an additive element in a total amount of 0.05 atomic% or more, and the total content of Cu and Sb, Zn, Sn, Pb, and Ti was 5.00 atomic% or less, the overetching amount was suppressed lower and the etching characteristics were excellent. The sheet resistance is sufficiently low, and the electrical characteristics of the metal film can be ensured. No hillock was observed after the heat treatment, and the heat resistance was excellent.

As described above, according to the examples of the present invention, it was confirmed that a metal film which can suppress the etching rate even when an etching solution containing nitric acid is used, can perform etching treatment with high accuracy, and can suppress aggregation of Ag due to heat, and a sputtering target used for forming the metal film can be provided.

Industrial applicability

Claims

1. A metal film characterized in that a metal film,

cu is contained in a range of 0.10 atomic% to 5.00 atomic%, the content of Pd is 40 mass ppm or less, the content of Pt is 20 mass ppm or less, the content of Au is 20 mass ppm or less, the content of Rh is 10 mass ppm or less, the total content of Pd, Pt, Au and Rh is 50 mass ppm or less, and the balance is composed of Ag and unavoidable impurities.

2. The metal film according to claim 1,

further, at least one or two or more of Sb, Zn, Sn, Pb, and Ti are contained as additive elements in a total amount of 0.05 atomic% or more, and the total content of Cu and Sb, Zn, Sn, Pb, and Ti is 5.00 atomic% or less.

3. A sputtering target characterized by comprising, in a sputtering target,

cu is contained in a range of 0.10 atomic% to 5.00 atomic%, the content of Pd is 40 mass ppm or less, the content of Pt is 20 mass ppm or less, the content of Au is 20 mass ppm or less, the content of Rh is 10 mass ppm or less, the total content of Pd, Pt and Rh is 50 mass ppm or less, and the balance is composed of Ag and unavoidable impurities.

4. The sputtering target according to claim 3,

5. The sputtering target according to claim 4,

based on the average value mu of the total content values of Sb, Zn, Sn, Pb and Ti in a plurality of measurement points of the sputtering surface_TAnd standard deviation sigma_TAnd a distribution D calculated by the following formula_TThe content of the organic acid is below 20 percent,

D_T＝(σ_T/μ_T)×100(％)。